环境科学与技术最新文献

The detection of noble gas radioisotopes following a suspected underground nuclear explosion is the surest indicator that nuclear detonation has occurred. However, the accurate interpretation and attribution of radioisotopic signatures is only possible with a complete understanding of transport processes occurring between the nuclear cavity and surface. In the far-field, diffusive forces contributing to gas transport are impacted by temperature gradients and subsurface lithology. In the current study, we investigate diffusive transport of xenon (Xe), krypton (Kr), and sulfur hexafluoride (SF₆) through intact Bandelier tuff at elevated temperatures using a newly developed high temperature diffusion cell. Diffusion coefficients determined using Finite Element Heat and Mass transfer code simulations and the Parameter ESTimation tool range from 2.6-3.1 × 10^-6 m²/s at 20 °C, 3.4-5.1 × 10^-6 m²/s at 40 °C, and 4.3-7.0 × 10^-6 m²/s at 70 °C. Sorption was found to be an important transport mechanism at ambient temperatures (20 °C). Most critically, our study shows that empirical porosity-based diffusion estimates for these gases through tuff captured neither the magnitude nor trends relative to a nonsorbing sandstone. These new insights highlight the importance of experimental transport investigations and will be used to improve models for subsurface gas propagation relevant to proliferation detection and environmental contamination.

Producing H₂O₂ through a selective, two-electron (2e) oxygen reduction reaction (ORR) is challenging, especially when it serves as an advanced oxidation process (AOP) for cost-effective water decontamination. Herein, we attain a 2e-selectivity H₂O₂ production using a carbon nanotube electrified membrane with ibuprofen (IBU) molecules laden (IBU@CNT-EM) in an ultrafast, single-pass electrofiltration process. The IBU@CNT-EM can generate H₂O₂ at a rate of 25.62 mol g_CNT^-1 h^-1 L^-1 in the permeate with a residence time of 1.81 s. We demonstrated that an interwoven, hydrophilic-hydrophobic membrane nanostructure offers an excellent air-to-water transport platform for ORR acceleration. The electron transfer number of the ORR for IBU@CNT at neutral pH was confirmed as 2.71, elucidating a near-2e selectivity to H₂O₂. Density functional theory (DFT) studies validated an exceptional charge distribution of the IBU@CNT for the O₂ adsorption. The adsorption energies of the O₂ and *OOH intermediates are proportional to the H₂O₂ selectivity (64.39%), higher than that of the CNT (37.81%). With the simple and durable production of H₂O₂ by IBU@CNT-EM electrofiltration, the permeate can actuate Fenton oxidation to efficiently decompose emerging pollutants and inactivate bacteria. Our study introduces a new paradigm for developing high-performance H₂O₂-production membranes for water treatment by reusing environmental functional materials.

Organophosphate esters (OPEs) have been observed in the remote Arctic Ocean, yet the influence of hydrodynamics and seasonal sea ice variations on the occurrence and transport of waterborne OPEs remains unclear. This study comprehensively examines OPEs in surface seawater of the central Arctic Ocean during the summer of 2020, integrating surface ocean current and sea ice concentration data. The results confirm significant spatiotemporal variations of the OPEs, with the total concentration of seven major OPEs averaging 780 ± 970 pg/L. Chlorinated OPEs, particularly tris(1-chloro-2-propyl) phosphate (TCPP), were dominant. The significant impact of hydrodynamics on the OPE transport is demonstrated by higher OPE concentrations in regions with strong surface currents, especially at the edge of the Beaufort Gyre and the confluence of the Beaufort Gyre and the Transpolar Drift. Furthermore, OPE levels were generally higher in drifting-ice-covered regions compared to ice-free regions, attributed to the volatilization of dissolved OPEs formerly trapped below the sea ice or newly released from melting snow and sea ice. Notably, TCPP decreased by only 19% in the ice-free area, while the more volatile triphenyl phosphate decreased by 63% compared with the partial ice region.

Resource demand by soil microorganisms critically influences microbial metabolism and then influences ecosystem resilience and multifunctionality. The ecological remediation of abandoned tailings is a topic of broad interest, yet our understanding of microbial metabolic status in restored soils, particularly at the aggregate scale, remains limited. This study investigated microbial resources within soil aggregates from revegetated tailings and applied a vector model of ecoenzymatic stoichiometry to examine how different vegetation patterns (grassland, forest, or bare land control) impact microbial resource limitation. Five-year vegetation restoration significantly elevated carbon (C) and nitrogen (N) concentrations and their stoichiometric ratios in soil aggregates (approximately 2-fold), although these increases were not translated to in the microbial biomass and its stoichiometry. The activities of C- and phosphorus (P)-acquiring extracellular enzymes in these aggregates increased substantially postvegetation, with the most pronounced escalation in macroaggregates (>0.25 mm). The vector model results indicated soil microbial metabolism was colimited by C and P, most acutely in microaggregates (<0.25 mm). This colimitation was exacerbated by monotypic vegetation cover but mitigated under diversified vegetation cover. Soil nutrient stoichiometric ratios in vegetation restoration controlled microbial resource limitation, overshadowing the impact of heavy metals. Our findings underscore that optimizing resource allocation within soil aggregates through strategic revegetation can enhance microbial metabolism in tailings, which advocates for the implementation of diverse vegetation covers as a viable strategy to improve the ecological development of degraded landscapes.

Wildfires are an increasing source of emissions into the air, with health effects modulated by the abundance and toxicity of individual species. In this work, we estimate reactive organic compounds (ROC) in western U.S. wildland forest fire smoke using a combination of observations from the 2019 Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) field campaign and predictions from the Community Multiscale Air Quality (CMAQ) model. Standard emission inventory methods capture 40-45% of the estimated ROC mass emitted, with estimates of primary organic aerosol particularly low (5-8×). Downwind, gas-phase species abundances in molar units reflect the production of fragmentation products such as formaldehyde and methanol. Mass-based units emphasize larger compounds, which tend to be unidentified at an individual species level, are less volatile, and are typically not measured in the gas phase. Fire emissions are estimated to total 1250 ± 60 g·C of ROC per kg·C of CO, implying as much carbon is emitted as ROC as is emitted as CO. Particulate ROC has the potential to dominate the cancer and noncancer risk of long-term exposure to inhaled smoke, and better constraining these estimates will require information on the toxicity of particulate ROC from forest fires.

Goethite often harbors impurities, such as phosphorus (P) and aluminum (Al), which are incorporated into its structure through direct substitution or coprecipitation with nanocrystalline phases. Understanding the processes that drive the release of P and Al from goethite is of paramount importance for the iron ore industry and for managing nutrient and pollutant behavior in the environment. This study investigates the impact of Fe(II)-catalyzed recrystallization on the release of P and Al from goethite. We evaluated the solubility and extractability of P and Al in suspensions of Al- and P-coprecipitated goethite, treated with ⁵⁷Fe-enriched Fe(II)_aq under oxygen-free conditions for 30 days at neutral pH and room temperatures. The addition of Fe(II)_aq induced the recrystallization of goethite dominant initial synthetic phases (i.e., low P- and Al-containing phases) and the transformation of higher P- and/or Al-bearing starting material that was actually a mixture of goethite and minor amounts of lepidocrocite and feroxyhyte. Our results reveal that Fe(II)-catalyzed mineral and structural evolution led to the repartitioning of P and, to a lesser extent, Al throughout the crystal structure, mineral surface, and aqueous solution. Following a 30 day reaction with Fe(II)_aq, we extracted approximately 80, 68.8, 73.9, and 83.2% of P from P-only, low, medium, and high P + Al goethite, respectively. Additionally, we observed total Al removals of approximately 17, 27, and 25% from low, medium, and high P + Al goethite, respectively. The results demonstrate that treating both P-only and P + Al goethite with Fe(II) at room temperature, followed by a 24 h extraction using 1 M NaOH, significantly enhances the overall extractability of P and Al, including both aqueous and surface-adsorbed fractions, compared to Fe(II)-free controls. These findings advance our understanding of the recrystallization process and impurity substitution in goethite, offering promising avenues for developing new environmentally friendly methods to extract P and other impurities from goethitic iron ores at lower temperatures.

As our planet grapples with the severe repercussions of plastic pollution, mechanical recycling has been proposed as a potential remedy. However, increasing mechanical recycling may have unintended negative consequences. For example, recycling of PVC flooring containing hazardous plasticizers that were used in the past may lead to continued exposure. Here we propose measures to increase recycling while circumventing adverse health impacts caused by legacy additives. For this, we conduct a dynamic substance flow analysis for Switzerland and the time period from 1950 to 2100, focusing on three plasticizers: di(2-ethylhexyl) phthalate (DEHP), diisononyl phthalate (DiNP), and di(2-ethylhexyl) terephthalate (DEHT). We quantify the uncertainty of results, check their plausibility against measured concentrations in samples representative for the Swiss market, and compare them with modeled substance flows in Germany. Based on the cross-checked model, future average concentrations of DEHP in PVC flooring on the Swiss market are expected to be above the legal limit of 0.1 wt % for several decades if increased recycling rates are implemented without additional measures. Phasing out the potentially concerning DiNP, too, and preventing phthalates from entering recycling would lower their average market concentrations to values below 0.1 wt % and enable increasing recycling rates without compromising product safety. Analogous measures could help achieve this goal across other European countries and product groups.

Particulate matter (PM) undergoing various aging processes in the atmosphere changes its toxicity. However, the mechanism of toxicity evolution is not fully clarified currently. This study demonstrates that photoaging promotes an increase in the oxidative potential (OP) of atmospheric PM by about 30%, and the increased OP is mainly attributed to the production of secondary organic compounds, while water-soluble metal ions contribute only 11%. The OP of nonextractable matters (NEMs) of atmospheric PM was mostly increased after photoaging, followed by water-soluble matters (WSMs). NEM can produce quinone-like functional groups and secondary persistent free radicals during photoaging, which are most likely to produce reactive oxygen species (ROS). For WSM, the conversion of low-oxidation humic-like substances (HULIS) to high-oxidation HULIS is the main reason for the increase in OP. Quinones, nitrophenols, and N-containing heterocycles are the OP contributors produced during the conversion process. Among them, quinones are the main secondary oxidizing active compounds, while nitro-phenolic compounds and N-containing heterocyclic compounds may play a catalyst-like role, facilitating the production of oxidizing active compounds and ROS in the newly converted high-oxidation HULIS. This study clarifies the secondary OP generation mechanism and provides new insights into the uncertainty of PM toxicity during atmospheric aging.

Recent concerns surrounding climate change and the contribution of fossil fuels to greenhouse gas (GHG) emissions have sparked interest and advancements in renewable energy sources including wind, solar, and hydroelectricity. These energy sources, often referred to as "clean energy", generate no operational onsite GHG emissions. They also offer the potential for clean hydrogen production through water electrolysis, presenting a viable solution to create an environmentally friendly alternative energy carrier with the potential to decarbonize industrial processes reliant on hydrogen. To conduct a full life cycle analysis, it is crucial to account for the embodied emissions associated with renewable and nuclear power generation plants as they can significantly impact the GHG emissions linked to hydrogen production and its derived products. In this work, we conducted a comprehensive analysis of the embodied emissions associated with solar photovoltaic (PV), wind, hydro, and nuclear electricity. We investigated the implications of including plant-embodied emissions in the overall emission estimates of electrolysis hydrogen production and subsequently on the production of synthetic ammonia, methanol, and Fischer-Tropsch (FT) fuels. Results show that average embodied GHG emissions of solar PV, wind, hydro, and nuclear electricity generation in the United States (U.S.) were estimated to be 37, 9.8, 7.2, and 0.3 g CO₂ e/kWh, respectively. Life cycle GHG emissions of electrolytic hydrogen produced from solar PV, wind, and hydroelectricity were estimated as 2.1, 0.6, and 0.4 kg of CO₂ e/kg of H₂, respectively, in contrast to the zero-emissions often used when the embodied emissions in their construction were excluded. Average life cycle emission estimates (CO₂ e/kg) of synthetic ammonia, methanol, and FT-fuel from solar PV electricity are increased by 5.5, 16, and 49 times, respectively, compared to the case when embodied emissions are excluded. This change also depends on the local irradiance for solar power, which can result in a further increase of GHG emissions by 35-41% in areas of low irradiance or reduce GHG emissions by 21-25% in areas with higher irradiance.